CN110217875A - Utilize stratiform MoS2Activate the method and application of persulfate removal butyl p-hydroxybenzoate - Google Patents
Utilize stratiform MoS2Activate the method and application of persulfate removal butyl p-hydroxybenzoate Download PDFInfo
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- CN110217875A CN110217875A CN201910385097.5A CN201910385097A CN110217875A CN 110217875 A CN110217875 A CN 110217875A CN 201910385097 A CN201910385097 A CN 201910385097A CN 110217875 A CN110217875 A CN 110217875A
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- bhb
- mos
- removal
- persulfate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Stratiform MoS is utilized the present invention relates to a kind of2Direct activation potassium hydrogen persulfate (PMS) and sodium persulfate (PDS) removal butyl p-hydroxybenzoate (BHB) method, specifically include: configuration pH be 3~10, the BHB target solution that concentration is 5 mg/L；Change experiment condition, a certain amount of business MoS is separately added into BHB target liquid2And PMS/PDS, it is placed under stirring condition and reacts.Present invention firstly discovers that: under the conditions of no external energy, stratiform MoS2Can direct activation persulfate generate living radical (SO simultaneously4 •‒、•OH and O2 •‒) and non-free radical (1O2) synergistic oxidation removal BHB.Process of the present invention process flow is simple, easily operated, not high to equipment requirement, stratiform MoS2Material is cheap and easy to get, has a vast market application potential in terms of emerging pollutant in processing water environment.
Description
Technical field
The invention belongs to two-dimensional layer chalcogenide materials and technical field of water pollution control, it is related to a kind of utilizing stratiform
MoS2Activate the method and application of persulfate removal butyl p-hydroxybenzoate.
Background technique
Currently, parabens (PBs) have caused as emerging environmental contaminants, domestic and international researcher's is wide
General concern.About 8000 tons of PBs are consumed in the whole world every year, and most PBs is introduced into production, use and treatment process
In environment；Report points out that PBs is detected extensively in wastewater treatment plant effluent, surface water and deposit, it is therefore necessary to be ground
Study carefully the technology of removal PBs.Jing Zhang etc. (Environ. Sci. Technol. 47,2013:13011) uses Ru/
CeO2It is catalyzed KMnO4Butyl p-hydroxybenzoate (BHB) in degradation water, experiment confirm Ru/CeO2The KMnO of catalysis4With efficient
The ability of degradation BHB.
Using metal oxide as activator or catalyst peroxynitrite decomposition hydrogen (H2O2) and persulfate (PS) formation activity is certainly
It is the hot subject of field of environment engineering by base degradation Organic substance in water.And using transient metal sulfide (TMDs) as activator
Or catalyst inducement generates the innovation and application that the pollutant in living radical degradation environment is then two-dimensional layer Material Field.Such as
Magnetic iron ore (FeS) can activate in PS inactivation waterE. coli2017 112:236 of K-12(Water Research), and two sulphur
Change molybdenum (MoS2) then it is used to the Bi that building has n-p hetero-junctions2O3/Bi2S3/MoS2Composite catalyst is to enhance photochemical catalytic oxidation
The performance (2017 200:47 of Applied Catalysis B:Environmental) of organic pollutants.MoS2Belong to
In hexagonal crystal system, have with layer structure as graphite-phase, interlayer is weaker Van der Waals force, be then in layer it is stronger covalently
Key, layer are easily peeled off with layer, therefore have good anisotropy and lower coefficient of friction.Sulphur atom has metal very strong
Adhesion strength makes MoS2Metal surface can be adhered well to and play lubricating function, MoS always2It is a kind of the inorganic of function admirable
Lubricant.In addition, stratiform MoS2It is also had been a great concern in the application of energy field.
Literature search the result shows that: under the conditions of no external energy, utilize stratiform MoS2The removal of direct activation persulfate
The method and its application of BHB have not been reported.Present invention firstly discovers that MoS2Can direct activation PMS/PDS generate simultaneously it is active freely
Base (SO4 •‒、•OH and O2 •‒) and non-free radical (1O2) synergistic oxidation removal BHB.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of utilization stratiform MoS2The method of direct activation persulfate.
Another object of the present invention is to provide the utilization stratiform MoS2Activate the living radical (SO that PMS/PDS is generated4 •‒、•
OH and O2 •‒) and non-free radical (1O2) synergistic oxidation removal BHB application.
The purpose of the present invention is realized by following technology path: a kind of to utilize stratiform MoS2Persulfate removal is activated to hydroxyl
The method of yl benzoic acid butyl ester, comprising the following steps: (1) configure pH be 3~10, the BHB target solution that concentration is 5 mg/L；
(2) change experiment condition, a certain amount of business MoS is separately added into BHB target liquid2And PMS/PDS, stirring.
The persulfate is PMS and PDS, and PDS is provided by Sinopharm Chemical Reagent Co., Ltd., specification are as follows: 500
G is bottled, purity > 98%；PMS is provided by Aladdin reagent Co., Ltd, specification are as follows: 500 g are bottled, and PMS chemical formula is
KHSO5•0.5KHSO4•0.5K2SO4, KHSO5Content >=47%.
The BHB pH value of solution is preferably that 3~10, PMS and SPS concentration are both preferably 2.5~7.5 mM.
The reaction condition is preferably that 15~40 DEG C of 300 rpm stirs 120~180 min.
It is described to utilize stratiform MoS2The method of activation persulfate removal butyl p-hydroxybenzoate is applied to go water removal dirty
Contaminate the mg/L of low concentration BHB(≤5 in environment).
The present invention has the following advantages and effect.
(1) present invention firstly discovers that in no external energy, MoS2Can direct activation PMS and PDS generate activity from
By base (SO4 •‒、•OH and O2 •‒) and non-free radical (1O2) efficiently remove BHB.
(2) MoS used in the present invention2, PMS and PDS it is cheap and easy to get, BHB removal reaction at normal temperatures and pressures can be into
Row, it is not high to equipment requirement, belong to Novel low-consumption water treatment technology.
(3) stratiform MoS used in the present invention2, PMS and PDS it is easily stored and transport, can be widely used for environmental pollution by water
It administers, there is biggish application prospect.
Detailed description of the invention
Fig. 1 is stratiform MoS2Activation PMS and PDS removes BPB curve synoptic diagram in water removal, and (illustration is stratiform MoS2Morphology characterization
Figure).
Fig. 2 is different quenchers to MoS2Activation PMS removes BHB effect tendency figure in water removal.
Fig. 3 is different quenchers to MoS2Activation PDS removes BHB effect tendency figure in water removal.
Specific embodiment
Present invention be described in more detail below by way of embodiments and drawings, and (scope of the present invention is not limited in described
Hold).
Embodiment 1
(1) stratiform MoS2Activation PMS and PDS goes BHB efficiency in water removal: compound concentration is the BHB aqueous solution of 5 mg/L, by its pH
It is adjusted to ~ 7.00.80 mL BHB aqueous solutions are measured respectively, and MoS is added after clean reaction flask, number2(1 g/L), PMS(5
MM) or PDS(5 mM), be placed in (25 ± 2 DEG C) of room temperature stirrings (300 rpm) and react 180 min, separated in time takes 2mL water
Sample is analyzed.
(3) the data obtained is depicted as curve graph, as shown in Figure 1: MoS2/ PMS and MoS2/ PDS system is equal in 180 min
Interior energy complete oxidation removes BHB；In addition, as seen from the figure, the MoS within entire reaction time2, PMS or PDS to the absorption of BHB or
The main reason for oxidation process is not its removal, the removal of BHB is mainly by stratiform MoS2It activates PMS and PDS and generates active oxygen
Species (see embodiment 2) Lai Shixian's.
Embodiment 2
(1) different quenchers are investigated to stratiform MoS2Activation PMS and PDS removes the influence of BHB efficiency and active specy point in water removal
Analysis: compound concentration is the BHB aqueous solution of 5 mg/L, its pH is adjusted to ~ 7.00.80 mL BHB aqueous solutions are measured respectively in cleaning
MoS is added after number in reaction flask2(1 g/L), PMS(5 mM) or PDS(5 mM)；Quencher, experiment sample difference is not added in control sample
0.5 M ethyl alcohol, the 0.5 M tert-butyl alcohol, 1 mM histidine or 1 mM 1,4-benzoquinone is added, is placed on (25 ± 2 DEG C) of room temperature stirrings (300
Rpm 180 min) are reacted, separated in time takes 2mL water sample to be analyzed.
(2) the data obtained is depicted as curve graph, as shown in Figure 2: 0.5 M ethyl alcohol and the 0.5 M tert-butyl alcohol are for MoS2/
PMS system removal BHB shows inhibiting effect, and the inhibition of 0.5 M ethyl alcohol is eager to excel than the 0.5 M tert-butyl alcohol, illustrates MoS2/
There are SO for PMS system4 •‒With•OH, and SO4 •‒BHB oxidation contribution is greater than•OH；1 mM histidine and 1 mM 1,4-benzoquinone for
MoS2/ PMS system removal BHB shows inhibiting effect, illustrates MoS2There is also O for/PMS system2 •‒With1O2；It is analyzed by Fig. 3
Know, 0.5 M ethyl alcohol, the 0.5 M tert-butyl alcohol, 1 mM histidine and 1 mM 1,4-benzoquinone are to MoS2/ PDS system removal BHB is shown
Strong inhibiting effect, illustrates MoS2/ PDS system also exists simultaneously SO4 •‒、•OH、O2 •‒With1O2Oxidation removal BHB.
Embodiment 3
(1) different initial pH, PMS/PDS dosages of solution and temperature are investigated to stratiform MoS2Activation PMS and PDS is gone in water removal
The influence of BHB efficiency: compound concentration is the BHB aqueous solution of 5 mg/L, its pH is adjusted to 3 ~ 10.80 mL BHB are measured respectively
MoS is added after clean reaction flask, number in aqueous solution2(1 g/L), the mM of PMS(2.5 ~ 7.5) or PDS(2.5 ~ 7.5
MM), it is placed on (15 ~ 40 DEG C) of room temperature stirrings (300 rpm) and reacts 180 min, separated in time takes 2mL water sample to carry out
Analysis.Analysis data are known: being in 3 ~ 10 ranges in pH, after reacting 180 min, 80% or more BHB can be by MoS2/ PMS and
MoS2/ PDS system oxidation removal；When pH ≈ 7, PMS and PDS dosage is when 2.5 ~ 7.5 mM change, BHB after 180 min
Oxidation removal rate can reach 98% or more；Increase solution temperature and is conducive to MoS2/ PMS and MoS2/ PDS system is quickly gone in water removal
BHB。
Claims (7)
1. a kind of utilize stratiform MoS2The method for activating persulfate removal butyl p-hydroxybenzoate, it is characterised in that this method
The following steps are included: configuration pH is 3~10, the BHB target solution that concentration is 5 mg/L；Change experiment condition, to BHB target liquid
In be separately added into a certain amount of business MoS2And PMS/PDS, stirring.
2. utilizing stratiform MoS according to claim 12The method for activating persulfate removal butyl p-hydroxybenzoate, it is special
Sign is: under the conditions of being not necessarily to external energy, stratiform MoS2It can direct activation persulfate generation living radical (SO4 •‒、•OH
And O2 •‒) and non-free radical (1O2) synergistic oxidation removal BHB.
3. utilizing stratiform MoS according to claim 12The method for activating persulfate removal butyl p-hydroxybenzoate, it is special
Sign is: layered MoS2It being provided by Sinopharm Chemical Reagent Co., Ltd., specification are as follows: 100 g are bottled, purity >
98%。
4. utilizing stratiform MoS according to claim 12The method for activating persulfate removal butyl p-hydroxybenzoate, it is special
Sign is: the persulfate is potassium hydrogen persulfate (PMS) and sodium persulfate (PDS), and PDS is had by Chinese medicines group chemical reagent
Limit company provides, specification are as follows: 500 g are bottled, purity > 98%；PMS is provided by Aladdin reagent Co., Ltd, specification are as follows:
500 g are bottled, and PMS chemical formula is KHSO5•0.5KHSO4•0.5K2SO4, KHSO5Content >=47%.
5. utilizing stratiform MoS according to claim 12The method for activating persulfate removal butyl p-hydroxybenzoate, it is special
Sign is: the MoS2Dosage is 1 g/L, and oxidant PMS/SPS concentration is 2.5~7.5 mM.
6. utilizing stratiform MoS according to claim 12The method for activating persulfate removal butyl p-hydroxybenzoate, it is special
Sign is: the reaction condition is that 15 ~ 40 DEG C of 300 rpm stirs 5~180 min.
7. utilizing stratiform MoS according to claim 12Activate the method application of persulfate removal butyl p-hydroxybenzoate
The mg/L of low concentration BHB(≤5 in removal environmental pollution by water).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624569A (en) * | 2019-09-14 | 2019-12-31 | 北京建筑大学 | MoS doped with metal ions2Method for degrading PPCPs by activating monopersulfate |
| CN111362391A (en) * | 2020-02-25 | 2020-07-03 | 暨南大学 | Novel method for removing organic pollutants through piezoelectric effect activation Fenton-like reaction |
| CN113135594A (en) * | 2020-01-19 | 2021-07-20 | 广东工业大学 | Persulfate activation method and application thereof |
| CN115215421A (en) * | 2022-08-16 | 2022-10-21 | 南华大学 | Application of vanadium tetrasulfide in degradation of organic pollutants |
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| CN105819562A (en) * | 2016-04-21 | 2016-08-03 | 中国科学院城市环境研究所 | Method for efficiently removing butyl 4-hydroxybenzoate by using MWCNTs-persulfate system high-efficiency and application of method |
| CN109019969A (en) * | 2018-08-22 | 2018-12-18 | 华东理工大学 | A kind of method of sulfide activation potassium hydrogen persulfate degradation of organic waste water |
| CN109553181A (en) * | 2018-12-11 | 2019-04-02 | 中国科学院生态环境研究中心 | A kind of method generated free radicals using trivalent molybdenum and its method for handling organic wastewater |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105819562A (en) * | 2016-04-21 | 2016-08-03 | 中国科学院城市环境研究所 | Method for efficiently removing butyl 4-hydroxybenzoate by using MWCNTs-persulfate system high-efficiency and application of method |
| CN109019969A (en) * | 2018-08-22 | 2018-12-18 | 华东理工大学 | A kind of method of sulfide activation potassium hydrogen persulfate degradation of organic waste water |
| CN109553181A (en) * | 2018-12-11 | 2019-04-02 | 中国科学院生态环境研究中心 | A kind of method generated free radicals using trivalent molybdenum and its method for handling organic wastewater |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624569A (en) * | 2019-09-14 | 2019-12-31 | 北京建筑大学 | MoS doped with metal ions2Method for degrading PPCPs by activating monopersulfate |
| CN113135594A (en) * | 2020-01-19 | 2021-07-20 | 广东工业大学 | Persulfate activation method and application thereof |
| CN113135594B (en) * | 2020-01-19 | 2023-07-25 | 广东工业大学 | Activation method of persulfate and application thereof |
| CN111362391A (en) * | 2020-02-25 | 2020-07-03 | 暨南大学 | Novel method for removing organic pollutants through piezoelectric effect activation Fenton-like reaction |
| CN115215421A (en) * | 2022-08-16 | 2022-10-21 | 南华大学 | Application of vanadium tetrasulfide in degradation of organic pollutants |
| CN115215421B (en) * | 2022-08-16 | 2023-08-25 | 南华大学 | Application of vanadium tetrasulfide in degrading organic pollutants |
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Application publication date: 20190910 |